Vat dyestuffs of the anthraquinone-2.1(n) benzacridone series



PatentedFeb. 18, 1936 UNITED STATES PATENT OFFICE 'VAT DYESTUFFS OF THEANTHRAQUINONE- 2.1 (N) BENZACRIDONE SERIES "Walter Bruck, Mannheim,Germany, assignor to General Aniline Works, Inc., New York,'N. Y., acorporation of Delaware No Drawing. Application January 3, 1933, SerialNo. 650,048. In Germany January 19, 1932 6 Claims.

" in which Xstands for halogen, and in which at '36 the dyestufiscontaining chlorine. The dyestuffs may be prepared for example bycondensing 1,3- dihalogenanthraquinone-Z-carboxylic acids or 1nitro-3-halogenanthraquinone 2 carboxylic acids or derivativessubstituted in the carboxyl group of the said "compounds for exampletheir esters, such as their methyl, ethyl, 'benzyl and phenyl esters,with anilines in which one ortho position to the amino group'isunoccupied and containing at least twohalogen atoms at least M6 one ofwhich is in the 3- or 5-position, and subsequent ring closure to form'acridones. The dyestufis may also be prepared by the action ofortho-aminobenzoic acids containing at least two halogen-atoms at leastone of which is in the 4- 150 or (i-position on1,3-dihalogenanthraquinones and subsequent ring [closure to formacridones. The ha1ogenanthraquinonebenzacridones of the :said =kind mayalso be obtained by introducing halogen into3-halogenanthraquinonebenzacrian; dones-which tmay already containhalogen in the Bz-ring. It is not necessary to carry outlthis treatmentin the presence of .halogenating'catalysts; substances of this kind,such as iodine,

- may, however, be used, if desired.

The following examples will further illustrate 6 the nature of thisinvention but the invention is not restricted to these examples. Theparts'are by weight.

Example 1 22 parts of 1,3-dichloranthranuinone-2-carboxylic acid benzyl'ester are heated to from 180 to 190 0., for about 5 hours with 12 partsof 2,3,4,5-vtetrachloraniline, 6 parts of anhydrous sodium acetate, 0.3part of copper oxide and 15 parts of nitrobenzene. After cooling, about200 parts of concentrated sulphuric acid are allowed to flow into thereaction mixture and it is then heated for an hour at about C. Thereaction mass is poured into water and the nitrobenzene 2o expelled withsteam. The remaining 1-tetrachloranilido -3-chloranthraquinone-Z-carboxylic acid is filtered off by suction anddried.

22 parts of this product are stirred at from 150 to 160 C. for about 2hours with parts of dry 25 nitrobenzene and 10 parts of aceticanhydride. The reaction mixture is then diluted with 85 parts of drynitrobenzene and 2.5 parts of concentrated sulphuric acid are slowlyintroduced at from to C. The temperature is kept at V 45 14 parts of1,3-dichloranthraquinone-2-carboxylic acid benzyl ester are heated atfrom to C. for 3 hours with 8 parts of metadichloramline, 3.6 parts ofanhydrous sodium acetate, 0.2 part of copper oxide and 35 parts of 50nitrobenzene. After cooling, about 100 parts of concentrated sulphuricacid are added to the reaction mixture which is then heated to 40 C. forashort time and introduced into water. The nitrobenzene is expelled withsteam and the 55 Example 4 If the 3,4,5-trichloraniline in Example 3 bereplaced by 2,4,5-trichloraniline, the remaining procedure in the saidexample being otherwise exactly followed, a tetrachloranthraquinone-2,1(N) -benzacridone having the formula:-

phuric acid are gradually added thereto at C.

The whole is stirred for about 4 hours at from to C., allowed to cooland the resulting 3-chlor-Bz,4,6-dichloranthraquinone-2,1 (N)benzacridone filtered off by suction. It is washed with nitrobenzene,freed from solvent by means of steam and freed from impurities solublein alkali by boiling with dilute caustic soda solution. The dyestuifdissolves in concentrated sulphuric acid giving an orange coloration andyields a violet vat. The dyestufi yields on cotton an orange dyeingwhich is at least twice as strong as the orange dyeing with the sameamount of the isomeric compound in which one chlorine atom is in the4-position of the anthraquinone nucleus instead of in the 3-position.

Example 3 10.3 parts of l,3-dichloranthraquinone-Z-carboxylic acidbenzyl ester are heated at from 180"v to 190 C. for 3 hours with 7.5parts of 3,4,5-trichloraniline, 2.7 parts of sodium acetate, 0.2 part ofcopper oxide and 35 parts of nitrobenzene. After cooling, about 100parts of concentrated sulphuric acid are allowed to flow in whilestirring, the whole is heated fora short time to 40 C. and the reactionmass poured into water. After distilling off the nitrobenzene withsteam, the resulting 1-trichloranilido-3-chloranthraquinone-2-carboxylicacid is filtered off by suction and dried.

14.2 parts of this product are stirred at from to C. for 3 hours with 50parts of nitrobenzene and 7 parts of acetic anhydride. The reactionmixture is then diluted with 50 parts of nitrobenzene and 1.7 parts ofconcentrated sulphuric acid are gradually introduced at from 95 to 100C. The temperature is kept constant for about 3 hours, the whole allowedto cool and the tetrachloranthraquinone benzacridone having the formula:

which separates out in the form of crystals, filtered off by suction. Itis washed with nitrobenzene, benzene, and ligroin and freed fromimpurities soluble in alkali by boiling with dilute caustic soda. Thedyestuif dissolves in concentrated sulphuric acid giving a redcoloration and dyes cotton from a violet vat brilliant yellowishredshades. In this case also there is a very great difference in strengthbetween the shades obtained with the said dyestuff and those obtainedwith the isomeric compound in which the chlorine atom is in the4-position of the anthraquinone nucleus instead of in the 3-position.

is obtained. It dissolves in concentrated sulphuric acid giving anorange-red coloration and yields a violet vat from which cotton is dyedsubstantially more bluish-red shades than when using the productobtained according to Example 3, but also has a much greater strength ofcolor as compared with the isomeric 4-Bz,3,5,6-trichloranthraquinone-2,l (N) -benzacridone.

Example 5 vigorously for about 3 hours at between 70 and 80 .C. and thenthe temperature is raised in the course of 3 hours up to 200 C. Thereaction mixture is allowed to cool and the reaction product is filteredoff by suction, washed with nitrobenzene and with benzene and ligroin,and recrystallized from trichlorbenzene. According to analysis itconsists mainly of triehlorodibromo' anthraquinone 2,1 (N) benzacridone.Probably the bromine atoms are contained in the 3- and fi-positions ofthe Bz-nucleus. The product dissolves in concentrated sulphuric acidgiving a red coloration from which it is precipitated by water in redflakes. The dyestufi dyes cotton red shades of good fastness propertiesfrom a violet vat.

What I claim is:--

1. Vat dyestufis of excellent fastness properties and tinctorial powercorresponding to the general formula H CO least two of the positionsmarked Y and Z are substituted by halogen atoms, at least one of whichstands in a position marked Y, said dyestuffs dissolving in concentratedsulphuric acid giving an orange to red coloration and giving a violetvat from which cotton is dyed orange to bluish-red shades.

2. Vat dyestuffs of excellent fastness properties and tinctorial powercorresponding tothe general formula EN Y o1 Ol HN/ c1 0 I oo dissolvingin concentrated sulphuric acid giving an orange-red coloration anddyeing cotton from a violet vat very strong brilliant red shades.

4. The vat dyestuil corresponding to the formula dissolving inconcentrated sulphuric acid giving an orange coloration and dyeingcotton from a violet vat very strong orange shades.

51. The vat dyestufi corresponding to the formu a EN 01 o I \/\Cl 0dissolving in concentrated sulphuric acid giving a red coloration anddyeing cotton from a violet vat strong brilliant yellowish-red shades.

6. The process of producing vat dyestuffs of the anthraquinone-2,l (N)-benzacridone series which comprises condensing a compound correspondingto the formula:

in which X stands for -OH or OR (R being alkyl or benzyl) with ananilinecorresponding to the formula:

HQN

said aniline containing at least two halogen atoms, at least one ofwhich stands in a position marked Y, at least one position marked Zbeing unsubstituted, and subjecting the condensation product to ringclosure to form an anthraquinone- 2,1 (N) -benzacridone.

WALTER BRUCK.

